EP2164904B1 - Polyetherimid-/polyphenylen-ether-sulfon-gemische - Google Patents

Polyetherimid-/polyphenylen-ether-sulfon-gemische Download PDF

Info

Publication number
EP2164904B1
EP2164904B1 EP08781489.3A EP08781489A EP2164904B1 EP 2164904 B1 EP2164904 B1 EP 2164904B1 EP 08781489 A EP08781489 A EP 08781489A EP 2164904 B1 EP2164904 B1 EP 2164904B1
Authority
EP
European Patent Office
Prior art keywords
composition
polyphenylene ether
equal
polyetherimide
linkages
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Revoked
Application number
EP08781489.3A
Other languages
English (en)
French (fr)
Other versions
EP2164904A1 (de
Inventor
Ganesh Kailasam
Robert R. Gallucci
Mark Alan Sanner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SABIC Global Technologies BV
Original Assignee
SABIC Global Technologies BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=39865740&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP2164904(B1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from US11/776,658 external-priority patent/US20090018242A1/en
Application filed by SABIC Global Technologies BV filed Critical SABIC Global Technologies BV
Publication of EP2164904A1 publication Critical patent/EP2164904A1/de
Application granted granted Critical
Publication of EP2164904B1 publication Critical patent/EP2164904B1/de
Revoked legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L81/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen or carbon only; Compositions of polysulfones; Compositions of derivatives of such polymers
    • C08L81/10—Polysulfonamides; Polysulfonimides

Definitions

  • blends of polyetherimide and polyphenylene ether sulfone are disclosed herein, methods for making the blends, and articles derived from such blends.
  • the blends have a particularly advantageous combination of properties.
  • Blends of two or more polymers can have a single phase (miscible blends) or multiple phases (immiscible or phase separated blends). Phase separated blends are complex and unpredictable. These blends can demonstrate a host of behaviors from delamination to excellent impact strength, from opacity to transparency. The complexity and unpredictability of phase separated, multiphase polymer systems is such that small changes in composition or processing can have a dramatic effect on one or more physical properties. Overall, this makes it very difficult to achieve a desired combination of properties as modifications to the polymer system to address one physical property can cause significant changes in another property.
  • polyetherimides have many valuable characteristics there is an increasing need for polymers or polymer blends with a combination of hydrolytic stability, high multiaxial impact energy, a high heat distortion temperature and a high modulus.
  • plastic resins that will survive high temperature sterilization and autoclaving.
  • retention of properties on exposure to repeated high temperature sterilization as many as 100, 500 and even 1000 cycles of sterilization at 130 to 138 °C, may be required.
  • adjuvants for example, morpholine or alkyl amines are added to the steam to prevent corrosion and protect the autoclave device and associated piping. Addition of these chemical bases to steam may further accelerate degradation of a thermoplastic resin placing even more performance demands on a suitable candidate resin.
  • such articles can also require other properties such as high impact to resist breakage in use. They also require heat resistance, in the form of a high heat distortion temperature to prevent melting or warping during sterilization. Additionally such articles will need high modulus and stiffness to give them the rigidly and strength for end use in devices such as trays, handles, bins, containers, animal cages, and connectors. In some instances having such devices that are transparent, so that the contents may be observed, is also useful.
  • thermoplastic composition comprising a phase separated blend, wherein the phase separated blend comprises 25 to 90 weight percent of a polyetherimide and 10 to 75 weight percent of a polyphenylene ether sulfone, wherein the weight percents are based on the combined weight of the polyetherimide and the polyphenylene ether sulfone.
  • the dispersed phase has an average cross sectional size of 0.01 to 10 micrometers.
  • the composition has a high impact strength and toughness with a multiaxial impact energy of greater than or equal to 45 foot pounds force (ft-lbs) (61 Joules (J)).
  • the composition demonstrates excellent hydrolytic stability by having a multiaxial impact energy of greater than or equal to 20 ft-lbs (27 J) after exposure to 130 to 138°C steam autoclaving for 300 hours.
  • the composition also has a tensile modulus of greater than 425,000 pounds per square inch (psi) (2,930 megaPascals (MPa)) and a heat distortion temperature (HDT) greater than or equal to 150°C. Also described herein are articles comprising the foregoing composition.
  • a composition comprises a phase separated blend having a dispersed phase average cross sectional size as described above.
  • the phase separated blend comprises a polyetherimide in an amount of 60 to 80 weight percent and a polyphenylene ether sulfone in an amount of 20 to 40 weight percent, based on the combined weight of polyetherimide and polyphenylene ether sulfone.
  • the composition has an initial multiaxial impact energy of greater than or equal to 45 ft-lbs (61 J), a multiaxial impact energy of greater than or equal to 20 ft-lbs (27 J) after exposure to 130 to 138°C steam autoclaving for 300 hours, a tensile modulus of greater than 425,000 pounds per square inch (2,930 MPa) and a heat distortion temperature (HDT) greater than or equal to 175°C. Additionally, the composition can have a percent transmission (%T) of greater than or equal to 50% at a thickness of 3.2 millimeters (mm).
  • a composition comprises a phase separated blend having a dispersed phase average cross sectional size as described above.
  • the phase separated blend comprises a polyetherimide in an amount of 60 to 80 weight percent and a polyphenylene ether sulfone in an amount of 20 to 40 weight percent, based on the combined weight of polyetherimide and polyphenylene ether sulfone.
  • the polyphenylene ether sulfone comprises repeating units having the formula wherein R is hydrogen, alkyl, aryl, alkyl aryl, alkoxy, halogen or combination thereof, x equals 0 to 4, and n equals 25 to 1000.
  • the aryl sulfone linkages are selected from the group consisting of 4,4' linkages, 3,3' linkages, 3,4' linkages, and mixtures thereof.
  • the polyetherimide and the polyphenylene ether sulfone each have a weight average molecular weight of 20,000 to 70,000 and the difference in molecular weight between the two polymers is less than 20% of the higher of the two molecular weights.
  • the composition has an initial multiaxial impact energy of greater than or equal to 45 ft-lbs (61 J), a multiaxial impact energy of greater than or equal to 20 ft-lbs (27 J) after exposure to 130 to 138°C steam autoclaving for 300 hours, a tensile modulus of greater than 425,000 pounds per square inch (2,930 MPa) and a heat distortion temperature (HDT) greater than or equal to 175°C.
  • a composition comprises a phase separated blend having a dispersed phase average cross sectional size as described above.
  • the phase separated blend comprises a polyetherimide in an amount of 60 to 80 weight percent and a polyphenylene ether sulfone in an amount of 20 to 40 weight percent, based on the combined weight of polyetherimide and polyphenylene ether sulfone.
  • the composition has an initial multiaxial impact energy of greater than or equal to 45 ft-lbs (61 J), a multiaxial impact energy of greater than or equal to 20 ft-lbs (27 J) after exposure to 130 to 138°C steam autoclaving for 300 hours, a tensile modulus of greater than 425,000 pounds per square inch (2,930 MPa) and a heat distortion temperature (HDT) greater than or equal to 175°C.
  • first,” “second,” and the like, “primary,” “secondary,” and the like, “(a),” “(b)” and the like, as used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another.
  • the terms “a” and “an” do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced item.
  • “Optional” or “optionally” means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where the event occurs and instances where it does not.
  • the endpoints of all ranges directed to the same component or property are inclusive of the endpoint and independently combinable.
  • alkyl is intended to include both C 1-30 branched and straight-chain, saturated aliphatic hydrocarbon groups having the specified number of carbon atoms.
  • alkyl include, but are not limited to, methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, t-butyl, n-pentyl, s-pentyl, n- and s-hexyl, n-and s-heptyl, and, n- and s-octyl.
  • aryl is intended to mean an aromatic moiety containing the specified number of carbon atoms, such as, but not limited to phenyl, tropone, indanyl or naphthyl.
  • the invention is based on the discovery that by using a specific combination of materials, in certain amounts, it is now possible to produce a composition (and articles) having a specific combination of useful properties, namely a composition (article) that initially exhibits a multiaxial impact energy of greater than or equal to 45 ft-lbs (61 J) and after 300 hours of steam autoclave exposure at 130 to 138 °C, the composition (article) has a multiaxial impact energy of greater than or equal to 20 ft-lbs (27 J); the composition also has a tensile modulus of greater than or equal to 425,000 psi (2930 MPa), and a heat distortion temperature of greater than or equal to 150°C.
  • phase separated blends are complex and unpredictable. Indeed, it can be very difficult to obtain a desired combination of physical properties in blends have multiple phases (phase separated blends) because modifications to the blend to affect a desired change in one property can have an unexpected negative impact on another physical property.
  • the composition disclosed herein comprises a phase separated blend.
  • the phase separated blend comprises a continuous phase and a dispersed phase.
  • the dispersed phase has an average cross section of 0.01 to 10 micrometers. Within this range the average cross section can be greater than or equal to 0.1, or, more specifically, greater than or equal to 0.3 micrometers. Also within this range the average cross section can be less than or equal to 5, or, more specifically, less than or equal to 3 micrometers.
  • the average cross section size is determined by transmission electron microscopy of injection molded samples stained with ruthenium tetraoxide.
  • the composition has a melt volume rate of 1.0 to 25.0 cubic centimeters per 10 minutes (cm 3 /10 minutes).
  • the composition has an improved hydrolytic stability when compared to polyetherimide alone.
  • the composition retains greater than or equal to 60% of the initial melt volume rate after being exposed to steam at 110 °C for 20 days. In some embodiments the composition retains greater than or equal to 70% of the initial melt volume rate.
  • "Initial melt volume rate" as used in this context refers to the melt volume rate of the composition immediately prior to exposure to steam at 110 °C for 20 days.
  • the composition also demonstrates a multiaxial impact energy of greater than or equal to 45 ft-lbs (61 J). Within this range the multiaxial impact energy can be greater than or equal to 50 ft-lbs (68 J), or, more specifically, greater than or equal to 55 ft-lbs (74 J). Also within this range the multiaxial impact energy can be less than or equal to 70 ft-lbs (95 J).
  • the composition has a tensile modulus of greater than or equal to 425,000 psi (2930 MPa). Within this range the tensile modulus can be greater than or equal to 450,000 psi (3103 MPa) or, more specifically, greater than or equal to 500,000 psi (3447 MPa). In some embodiment the tensile modulus is less than or equal to 600,000 (4137 MPa).
  • the composition has a heat distortion temperature of greater than or equal to 150°C, or, more specifically, greater than or equal to 175°C, or, even more specifically greater than or equal to 190°C.
  • the heat distortion temperature can be less than or equal to 300°C.
  • the composition has a refractive index (RI) of 1.620 to 1.670.
  • RI refractive index
  • both the polyphenylene ether sulfone and the polyetherimide have an RI of 1.620 to 1.670.
  • the refractive index can be greater than or equal to 1.625, or, more specifically, greater than or equal to 1.630. Also within this range the refractive index can be less than or equal to 1.665, or, more specifically, less than or equal to 1.660.
  • the composition comprises a transparent phase separated blend.
  • the percent transmittance (%T) on a 3.2 mm thick article can be greater than or equal to 50%, or, more specifically, greater than or equal to 70%.
  • the %T can be less than 90%.
  • Percent haze (%H) can be less than or equal to 10%, or, more specifically, less than or equal to 5%.
  • polyetherimide/polyphenylene ether sulfone blends show good melt compatibility such that when compounded or extruded they can be formed into strands and pelletized without excessive die swell, surging, delamination, skinning, or strand breakage.
  • Polyetherimide resins may comprise more than 1, typically 10 to 1000, or, more specifically, 10 to 500 structural units, of the formula (1) wherein R 1 includes but is not limited to substituted or unsubstituted divalent organic groups such as: (a) aromatic hydrocarbon groups having 6 to 24 carbon atoms and halogenated derivatives thereof; (b) straight or branched chain alkylene groups having 2 to 20 carbon atoms; (c) cycloalkylene groups having 3 to 24 carbon atoms, or (d) divalent groups of formula (2) defined below.
  • R 1 includes but is not limited to substituted or unsubstituted divalent organic groups such as: (a) aromatic hydrocarbon groups having 6 to 24 carbon atoms and halogenated derivatives thereof; (b) straight or branched chain alkylene groups having 2 to 20 carbon atoms; (c) cycloalkylene groups having 3 to 24 carbon atoms, or (d) divalent groups of formula (2) defined below.
  • T is -O- or a group of the formula -O-Z-O- wherein the divalent bonds of the -O- or the -O-Z-O- group are in the 3,3', 3,4', 4,3', or the 4,4' positions.
  • Z includes, but is not limited to, substituted or unsubstituted divalent organic groups such as: (a) aromatic hydrocarbon groups having about 6 to about 20 carbon atoms and halogenated derivatives thereof; (b) straight or branched chain alkylene groups having about 2 to about 20 carbon atoms; (c) cycloalkylene groups having about 3 to about 20 carbon atoms, or (d) divalent groups of the general formula (2); wherein Q includes but is not limited to a divalent moiety selected from the group consisting of -O-, -S-, -C(O)-, -SO 2 -, -SO-, -C y H 2y - (y being an integer from 1 to 8), and fluorinated derivatives thereof, including perfluoroalkylene groups.
  • Z may comprise exemplary divalent groups of formula (3)
  • the polyetherimide may be a copolymer. Mixtures of polyetherimides may also be employed.
  • the polyetherimide can be prepared by any of the methods well known to those skilled in the art, including the reaction of an aromatic bis(ether anhydride) of the formula (4) with an organic diamine of the formula (5) H 2 N-R 1 -NH 2 (5) wherein T and R 1 are defined as described above.
  • aromatic bis anhydrides examples include:
  • Another class of aromatic bis(ether anhydride)s included by formula (4) above includes, but is not limited to, compounds wherein T is of the formula (6) and the ether linkages, while shown in the 4,4' positions may also be in the 3,3', 3,4', or 4,3' positions and where Q is as defined above.
  • organic diamines examples include ethylenediamine, propylenediamine, trimethylenediamine, diethylenetriamine, triethylene tetramine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, decamethylenediamine, 1,12-dodecanediamine, 1,18-octadecanediamine, 3-methylheptamethylenediamine, 4,4-dimethylheptamethylenediamine, 4-methylnonamethylenediamine, 5-methylnonamethylenediamine, 2,5-dimethylhexamethylenediamine, 2,5-dimethylheptamethylenediamine, 2, 2-dimethylpropylenediamine, N-methyl-bis (3-aminopropyl) amine, 3-methoxyhexamethylenediamine, 1,2-bis(3-aminopropoxy) ethane, bis(3-aminopropyl) sulfide, 1,4-cyclo
  • the organic diamine comprises m-phenylenediamine, p-phenylenediamine, sulfonyl dianiline, or a combination comprising one or more of the foregoing.
  • the polyetherimide resin comprises structural units according to formula (1) wherein each R 1 is independently p-phenylene or m-phenylene or a mixture thereof and T is a divalent group of the formula (7)
  • R 1 is independently p-phenylene or m-phenylene or a mixture thereof
  • T is a divalent group of the formula (7)
  • Included among the many methods of making polyetherimides are those disclosed in US Patents 3,847,867 , 3,852,242 , 3,803,085 , 3905,942 , 3,983,093 , 4,443,591 and 7,041,773 .
  • Some polyetherimide (PEI) materials are described in ASTM D5205-96 Standard Classification System for Polyetherimide Materials.
  • Polyetherimides may have a melt index of 0.1 to 10 grams per minute (g/min), as measured by American Society for Testing Materials (ASTM) D1238 at 340 to 370 °C, using a 6.7 kilogram (kg) weight.
  • the polyetherimide resin has a weight average molecular weight (Mw) of 10,000 to 150,000 grams per mole (g/mole), as measured by gel permeation chromatography, using polystyrene standards.
  • Mw weight average molecular weight
  • Mw weight average molecular weight
  • the polyetherimide has Mw of 20,000 to 70,000.
  • Such polyetherimide resins typically have an intrinsic viscosity greater than 0.2 deciliters per gram (dl/g), or, more specifically, 0.35 to 0.7 dl/g as measured in m-cresol at 25 °C.
  • the polyetherimide is present in an amount of 25 to 90 weight percent, based on the combined weight of polyetherimide and polyphenylene ether sulfone. Within this range the polyetherimide may be present in an amount greater than or equal to 50 weight percent, or, more specifically, greater than or equal to 60 weight percent. Also within this range the polyetherimide may be present in an amount less than or equal to 90 weight percent, or, more specifically, less than or equal to 85 weight percent.
  • Polyphenylene ether sulfones comprise repeating units having both an ether linkage and an aryl sulfone linkage in the backbone of the polymer as shown in formula (8) wherein R is hydrogen, alkyl, aryl, alkyl aryl, alkoxy, halogen or combination thereof, x equals 0 to 4, and n equals 25 to 1000, or, more specifically, n equals 25 to 500, or, more specifically, n equals 25 to 100.
  • the aryl sulfone linkages maybe 4,4', 3,3', 3,4' or mixtures thereof.
  • the aryl sulfone linkages are 4,4' diaryl sulfone.
  • greater than or equal to 50 mole percent of the main chain sulfone linkages are derived from biphenol.
  • the polyphenylene ether sulfone is a polyphenylene ether sulfone copolymer of formula (10) wherein A is a linking group selected from, -O-, -S-, -SO 2 -, C 6 -C 18 aryl, and C 3 -C 12 alkyl. In some embodiments A is isopropylidene. Linkages of A to the aryl groups may be at the 4,4', 3,3', 3,4' positions or mixtures thereof. In many embodiments the linkages are at the 4,4' positions.
  • R and x are defined as above; n > m, and n+ m equals 20 to 1000, or, more specifically n + m equals 25 to 500, or, even more specifically, n +m equals 25 to 100.
  • Aryl sulfone linkages may be at the 4,4', 3,3', 3,4' positions or mixtures thereof. In many embodiments the linkages are at the 4,4' positions.
  • the polyphenylene ether sulfones have n equal to 70% and m equal to 30% based on the total of n + m. In some embodiments n equals 80% and m equals 20%, based on the total of n + m.
  • Exemplary aromatic dihydroxy compounds that can be used to make the polyphenylene ether sulfone copolymers include bisphenols and biphenols such as bisphenol A, dimethyl cyclohexyl bisphenol, dihydroxy diphenyl ether, hydroquinone, methyl hydroquinone and 4,4'-biphenol.
  • Other exemplary aromatic dihydroxy compounds are disclosed in U.S. Patent Publication Nos. 2006/0167216 , 2005/0113558 , and 2006/0069236 .
  • the polyphenylene ether sulfone can comprise a homopolymer, copolymer, or combination thereof.
  • Copolymers include random copolymers, non-random copolymers and block copolymers.
  • Polyphenylene ether sulfones are commercially available, including the polycondensation product of biphenol with dichloro diphenyl sulfone.
  • An example is PPSU resin is RADELTM R, available from Solvay, Inc.
  • the carbonate method in which a dihydric phenol and a dihalobenzenoid compound are heated, for example, with sodium carbonate or bicarbonate and a second alkali metal carbonate or bicarbonate is also disclosed in the art, for example in US Patents 4,176,222 .
  • the polyphenylene ether sulfone may be prepared by any of the variety of methods known in the art including those described in the U.S. Patent Publications referenced above.
  • the molecular weight of the polyphenylene ether sulfone can be greater than or equal to 0.3 dl/g, or, more specifically, greater than or equal to 0.4 dl/g and, typically, will not exceed 1.5 dl/g.
  • the polyphenylene ether sulfone weight average molecular weight can be 10,000 to 100,000 grams per mole (g/mol) as determined by gel permeation chromatography using ASTM D5296 with polystyrene standards. In some embodiments the polyphenylene ether sulfone weight average molecular weight can be 20,000 to 70,000 grams per mole (g/mol). Polyphenylene ether sulfones may have glass transition temperatures of 180 to 250 °C.
  • the polyphenylene ether sulfone is present in an amount of 10 to 75 weight percent, based on the combined weight of the polyetherimide and the polyphenylene ether sulfone. Within this range the poly polyphenylene ether sulfone may be present in an amount greater than or equal to 20 weight percent, or, more specifically, greater than or equal to 30 weight percent. Also within this range the polyphenylene ether sulfone may be present in an amount less than or equal to 60 weight percent or, more specifically, less than or equal to 50 weight percent.
  • Another aspect of the invention is a method to make polyphenylene ether sulfones/polyetherimide blends with the stability needed for melt processing such that there is relatively little molecular weight change during the melting and article forming procedure. This requires that each polymer be essentially free of linkages that will react in the melt to change molecular weight. The presence of benzylic protons in polyphenylene ether sulfones and polyetherimides typically accelerates reactions that change the polymer's molecular weight in the melt.
  • polyphenylene ether sulfone and polyetherimide blends with structural units derived from aromatic diamines, aromatic dianhydrides, bisphenols, or diaryl sulfones and capping agents essentially free of benzylic protons may be preferred in some applications, especially those involving isolation from the melt and melt processing after polymerization.
  • "essentially free of benzylic protons" means that the polyphenylene ether sulfones and polyetherimides have less than 5 mole % of structural units, or, less than 3 mole % structural units, or, less than 1 mole % structural units derived from monomers and/or end cappers containing benzylic protons.
  • the polyphenylene ether sulfone and the polyetherimide are free of benzylic protons.
  • Polyetherimides and polyphenylene ether sulfones can have low levels of residual volatile species, such as residual solvent and/or water.
  • the polyetherimide and the polyphenylene ether sulfone each have a residual volatile species concentration of less than 1000 parts by weight per million parts by weight (ppm), or, more specifically, less than 500 ppm, or, more specifically, less than 300 ppm, or, even more specifically, less than 100 ppm.
  • the composition has a residual volatile species concentration of less than 1000 parts by weight per million parts by weight (ppm), or, more specifically, less than 500 ppm, or, more specifically, less than 300 ppm, or, even more specifically, less than 100 ppm.
  • halogenated aromatic compounds such as chloro benzene, dichloro benzene, trichloro benzene, aprotic polar solvents such as dimethyl formamide (DMF), N-methyl pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), diaryl sulfones, sulfolane, pyridine, phenol, veratrole, anisole, cresols, xylenols, dichloro ethanes, tetra chloro ethanes, pyridine and mixtures thereof.
  • aprotic polar solvents such as dimethyl formamide (DMF), N-methyl pyrrolidinone (NMP), dimethyl sulfoxide (DMSO), diaryl sulfones, sulfolane, pyridine, phenol, veratrole, anisole, cresols, xylenols, dichloro ethanes, tetra chloro ethan
  • Low levels of residual volatile species in the final polymer product can be achieved by known methods, for example, by devolatilization or distillation.
  • the bulk of any solvent may be removed and any residual volatile species may be removed from the polymer product by devolatilization or distillation, optionally at reduced pressure.
  • the polymerization reaction is taken to some desired level of completion in solvent and then the polymerization is essentially completed and most remaining water is removed during at least one devolatilization step following the initial reaction in solution.
  • Apparatuses to devolatilize the polymer mixture and reduce solvent and other volatile species to the low levels needed for good melt processability are generally capable of high temperature heating under vacuum with the ability to rapidly generate high surface area to facilitate removal of the volatile species.
  • the mixing portions of such apparatuses are generally capable of supplying sufficient power to pump, agitate and stir the high temperature, amorphous polyphenylene ether sulfone and polyetherimide melt which may be very viscous.
  • Suitable devolatilization apparatuses include, but are not limited to, wiped films evaporators, for example those made by the LUWA Company and devolatilizing extruders, especially twin screw extruders with multiple venting sections, for example those made by the Werner Pfleiderer Company or Welding Engineers.
  • the polyetherimide and the polyphenylene ether sulfone each have a weight average molecular weight (Mw) of 20,000 to 70,000 grams per mole (g/mol) where the difference in molecular weight between the two polymers is less than 20% of the higher of the molecular weights. In some embodiments the difference in molecular weight between the two polymers is less than 10% of the higher of the molecular weights.
  • Mw weight average molecular weight
  • g/mol grams per mole
  • the polyetherimide has a glass transition temperature of 200 to 280°C and the polyphenylene ether sulfone has a glass transition temperature of 200 to 250°C.
  • melt filtering can occur during initial resin isolation or in a subsequent step.
  • Blends of polyetherimide and polyphenylene ether sulfones or polyphenylene ether sulfone copolymers can be melt filtered in the same extrusion operation where they are blended together.
  • Melt filtering can be performed using a filter with pore size sufficient to remove particles with a dimension of greater than or equal to 100 micrometers or with a pore size sufficient to remove particles with a dimension of greater than or equal to 40 micrometers.
  • the composition may optionally comprise additives such as UV absorbers; stabilizers such as light stabilizers and others; lubricants; plasticizers; pigments; dyes; colorants; anti-static agents; foaming agents; blowing agents; metal deactivators; and combinations comprising one or more of the foregoing additives.
  • Antioxidants can be compounds such as phosphites, phosphonites, hindered phenols or mixtures thereof. Phosphorus containing stabilizers including triaryl phosphite and aryl phosphonites are of note as useful additives. Difunctional phosphorus containing compounds can also be employed.
  • the phosphorus containing stabilizers with a molecular weight greater than or equal to 500 g/mole, but less than or equal to 5,000 g/mole, are useful.
  • the additive can comprise hindered phenols with molecular weight over 500 g/mole.
  • the additive can include mixtures of a mold release agent and a stabilizer selected from the group consisting of phosphite stabilizers, phosphonite stabilizers, hindered phenol stabilizers, and combinations thereof. Phosphorus containing stabilizers may be present in the composition at 0.01 to 1.0% by weight of the total composition.
  • the composition can optionally comprise a mold-release agent.
  • the mold-release agents include, but are not limited to, natural and synthetic paraffins, polyethylene waxes, fluorocarbons, and other hydrocarbon mold-release agents; stearic acid and other higher fatty acids; stearic acid amide, ethylene bis stearamide, and other fatty acid amides, alkylene bis fatty acid amides, and other fatty acid amide mold-release agents; butyl stearate, pentaerythritol tetrastearate, and other alcohol esters of fatty acid, polyhydric alcohol esters of fatty acid, and other fatty acid ester mold release agents; silicone oil and other silicone mold release agents, and mixtures of any of the aforementioned.
  • a mold release agent selected from the group consisting of C 15 to C 30 carboxylic acids, C 15 to C 30 aliphatic carboxylic amides and mixtures thereof are employed.
  • the mold release agent can be used in conjunction with other additives, e.g., polytetrafluoroethylene, fiber glass, minerals, including nano scale minerals, pigments, colorants, carbon fibers, ceramic fibers.
  • the amount of the mold release agent can be greater than or equal to 0.1 weight percent, based on the total weight of the composition. In one embodiment, the amount of the mold release agent is 0.1 to 2 weight percent, based on the total weight of the composition. In another embodiment, the amount of the mold release agent is 0.3 to 1 weight percent, based on the total weight of the composition.
  • the polyetherimide/polyphenylene ether sulfone blends may also comprise other polymers such as polysulfones, polyethersulfones, silicone polyetherimides, polyamides, polyphenylene ethers, polyolefins, and mixtures thereof, provided that they are used in such amount as not to compromise the multiaxial impact energy, tensile modulus and heat distortion temperature properties enumerated herein.
  • polymers can be added to the composition in amounts of 1 to 40 weight percent, or, 1 to 30 weight percent, or, 1 to 20 weight percent, based on the total weight of the composition.
  • the thermoplastic composition can be prepared by melt mixing or a combination of dry blending and melt mixing.
  • Melt mixing can be performed in single or twin screw type extruders or similar mixing devices that can apply a shear and heat to the components.
  • Melt mixing can be performed at temperatures greater than or equal to the melting temperatures of the polyetherimide and polyphenylene ether sulfone and less than the degradation temperatures of any of the components of the composition.
  • suitable melt mixing is achieved at a temperature of 125 to 150°C above the highest glass transition temperature of the two polymers.
  • All of the ingredients may be added initially to the processing system. In some embodiments, the ingredients may be added sequentially or through the use of one or more master batches.
  • compositions described above can be used to make articles (including portions of articles).
  • Articles can be made by any suitable method, e.g., injection molding, compression molding, sintering, thermoforming, blow molding, profile extrusion, melt spinning, gas assist molding, foam molding, rotomolding, solvent casting, and the like.
  • Exemplary articles comprising the polyetherimide/polyphenylene ether sulfone composition include molded parts, sheets, slabs, profiles, films or fibers.
  • the articles can also include medical devices, membranes, surgical instrument trays, handles, animal cages, part of a water supply, sterilization or decontamination system, part of a device or system for collecting, transporting or handling beer, wine, milk, cheese, or other dairy products.
  • the article may be particularly useful especially where the use temperature is equal to or greater than 40°C, or greater than or equal to 80°C.
  • Such articles can be used in food preparation especially where moisture and high temperatures are encountered.
  • Articles can also be a lighting device, reflector, metallized reflector, helmet or other protective device, fire helmets, face shields, safety glasses, eyeglasses.
  • the article can also be any energy absorbing safety devices.
  • Articles may also be used in food service, storage or preparation. Our composition will be especially useful in any article requiring steam sterilization after use, especially repeated sterilization.
  • compositions are further described by the following non-limiting examples.
  • PEI contained 0.1 weight percent hindered phenol (IRGANOX 1010) and 0.1 weight percent tris (di-2,4 -tert butyl phenyl) phosphite (IRGAPHOS 168).
  • BPADA bisphenol- A dianhydride
  • DDS 4,4'-diamino diphenyl sulfone
  • Blends were prepared by extruding of mixtures of the polyphenylene ether sulfones and polyetherimides in a 2.5 inch (63.5 mm) single-screw vacuum vented extruder. Compositions are listed in weight percent based on the total weight of the composition except where noted otherwise.
  • the extruder was set at about 325 to 360 °C.
  • the blends were run at about 180 rotations per minute (rpm) under vacuum using a mild mixing screw; vacuum was approximately 20 inches (508 mm) of mercury (Hg). In some instances the blend was melt filtered using a 40 micrometers filter.
  • the extrudate was cooled, pelletized and dried at 135 °C. Test samples were injection molded at a set temperature of 350 to 375 °C and mold temperature of 120 °C, a screw speed of approximately 60 rpm, with 50 psi (0.345 Mpa) back pressure using a 30 seconds cycle time.
  • Percent transmittance (%T) and percent haze (%H) were measured as per ASTM D1003 on 3.2 mm thick injection molded samples. Multiaxial impact energy was measured as total energy according to ASTM D3763 on 102 x 3.2 mm discs using a DYNATUP apparatus; velocity was 3.3 meters/second.
  • Transmission electron micrographs were obtained for some examples.
  • the samples were microtomed from injection molded bars in a direction perpendicular to flow.
  • the microtomed sections were stained with ruthenium tetraoxide (RuO 4 ).
  • the lighter continuous phase is the polyetherimde.
  • the darker phase is the polyphenylene ether sulfone.
  • the black bar in each figure represents 0.5 micrometers (microns).
  • Examples 1, 2 and 3 The purpose of Examples 1, 2 and 3 was to evaluate how different inventive blends performed as compared to PPSU and PEI, individually, as well as how inventive blends performed as compared to other blends of PEI and PPSU. More particularly, Table 1 shows molded properties of PPSU (control A), PEI (control B) as well as their blends.
  • the PPSU (control A) showed very low tensile strength and tensile modulus below 425 Kpsi.
  • the PEI (control B) was deficient in impact strength for many applications with multiaxial impact energy below 45 ft-lbs. Addition of 3 or 5 wt.% PPSU (controls C and D) had little beneficial effects.
  • Blends with higher amounts of PPSU showed a good balance of impact and stiffness, with multiaxial impact energy higher than either PEI or PPSU. Modulus was much improved over PPSU.
  • the blends used in Examples 1, 2 and 3 also showed good elongation at break (greater than 50%). Heat distortion under a heavy load (264 psi, 1.8 MPa) is still very good, (greater than 195°C). Blends of Examples 1, 2 and 3 were easy to extrude and gave uniform strands that did not show die swell or surging seen in other PEI-Polysulfone blends.
  • Injection molded articles of Examples A, B, 1,2 and 3 were subjected to autoclave testing at 134 °C using steam containing 50 ppm morpholine. Samples were tested after 250, 500, 750 and 1000 cycles. For each cycle steam exposure time was 20 minutes. The articles were tested for tensile and multiaxial impact energy properties. Results are shown in Table 2.
  • the PEI (B) had high tensile modulus which was retained after autoclaving, but the multiaxial impact energy and elongation at break decreased on exposure to 134 °C steam after a little as 250 cycles.
  • the PPSU (A) showed good retention of impact but had low tensile modulus.
  • Examples 1, 2 and 3 showed that multiaxial impact energy that was higher than either control. Even after 1000 cycles multiaxial impact strength was still greater than 20 ft-lbs (27 J) even with as little as 20 weight percent PPSU in the blend (Example 1). Examples 1, 2 and 3 had all retained their superior tensile modulus and show superior elongation at break than the PEI (B) after 134 °C steam exposure. The blends (Examples 1, 2 and 3) all had good retention of initial transparency and low haze after autoclaving.
  • Comparative Examples E, F, and G were evaluated the performance of PEI and PSU blends.
  • Examples E, F and G blends of PEI and PSU were examined. Results are shown in Table 3.
  • Table 3 E F G PSU 20 30 40 PEI 80 70 60 Blends E, F and G surged and swelled at the die when extruded and could not be processed into pellets
  • Examples 4, 5 and 6 The purpose of Examples 4, 5 and 6 was to show how blends of PPSU-PEI performed after being exposed to aging conditions.
  • Table 4 shows blends of PPSU-PEI (Examples 4, 5 and 6) that were aged in a pressure cooker at 110 °C for 20 days using deionized water: Table 4 B 4 5 6 PEI 100 90 50 10 PPSU 10 50 90 MVR 0 Day 7.2 8.8 8.2 6.6 MVR 20 Days 11.1 11.0 8.1 6.8 % Change 54 25 1 3
  • melt volume rate (MVR) measured at 337°C and reported in cm 3 /10 minutes showed a large increase for the PEI control (B) indicating degradation of the PEI polymer.
  • the PEI-PPSU blends of Examples 4, 5 and 6 showed much smaller change of MVR indicating better stability when exposed to 110 °C steam. Even a low level (10 weight percent) of PPSU gave protection against MVR loss.
  • Examples 7-12 were to evaluate the performance of PEI-PPSU blends. Results are shown in Table 5. Table 5 7 8 9 10 11 12 PEI 80.0 79.8 75.0 74.8 60.0 59.8 PPSU 20.0 20.0 25.0 25.0 40.0 40.0 Erucamide - 0.2 - - - - Stearic Acid - - - 0.2 - 0.2 Tensile Strength at Yield in Kpsi (MPa) 14.5 (100) 14.7 (101) 14.5 (100) 14.3 (99) 13.9 (96) 14.2 (98) Tensile Modulus in Kpsi (MPa) 536 (3695) 525 (3620) 492 (3392) 491 (3385) 484 (3337) 490 (3378) Tensile Elongation at Break in % 83 90 93 95 93 95 Multiaxial Impact Energy Total Energy @ 73°F (23°C) in ft-lbs (J) 61.2 (83) 63.3 (86) 44.8 (61) 50.4 (68) 56.6 (77
  • Example 8 showed the addition of 0.2 weight percent of an alkyl carboxylic amide, erucamide, which acts to modify surface properties such as mold release. Note the high %T and low %H, high tensile modulus and high multiaxial impact energy of Example 7, with no euracamide, was retained in Example 8 with the euracamide. Similarly Examples 10 and 12 with 0.2 weight percent of an alkyl fatty acid, stearic acid, which also acted to modify surface properties such as mold release, demonstrated good retention of properties observed in PPSU-PEI blends Examples 9 and 11 with no stearic acid.
  • Comparative Example H and Example 13 were to evaluate the performance of a blend containing PEI and a PPSU-PSU copolymer.
  • the copolymer had 20 mole % BPA and 80 mole% biphenol polymer made by reaction with dichloro diphenyl sulfone. Results are shown in Table 6.
  • the copolymer blends (13) had high multiaxial impact energy, and tensile modulus, good elongation, and high transparency with low haze.
  • the PEI-PPSU-PSU copolymer blend (13) performance was similar to the performance of the PPSU homopolymer-PEI blend (11).
  • Comparative Example I and EXAMPLES 14-15 were to evaluate the performance of blends containing PPSU and polyetherimide sulfone. Results are shown in Table 8. Table 8 I 14 15 PEIS 100 90 50 PPSU 0 10 50 Tensile Strength at Yield n Kpsi (MPa) 13.5 (93) 13.2(91) 12.5 (86) Tensile Modulus in Kpsi (MPa) 524 (3613) 512 (3530) 466(3213) Tensile Elongation at Break in % 4 4 21 Multiaxial Impact Energy at 73°F (23°C) in ft-lbs (J) 10.0 (13) 21.9 (30) 50.8 (69) At 32°F (0°C) in ft-lbs (J) 9.4 (13) 17.6 (24) 50.1 (68) HDT 264 psi (1.8 MPa)in °C 218 217 210 %Haze 6.6 6.4 9.2 %Transmission 35 41 48 Melt Flow Rate at 337°C,
  • the PEIS-PPSU blend shows high tensile modulus versus PPSU and improved multiaxial impact energy over the PEIS. Multiaxial impact energy is retained at low temperature. Note the higher HDT than in the PEI-PPSU blends.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (15)

  1. Zusammensetzung, die ein phasengetrenntes Gemisch umfasst, das Folgendes umfasst:
    25 bis 90 Gewichtsprozent eines Polyetherimids und
    10 bis 75 Gewichtsprozent eines Polyphenylenethersulfons;
    wobei das phasengetrennte Gemisch eine dispergierte Phase mit einem durchschnittlichen Querschnitt von 0,01 bis 10 Mikrometer umfasst;
    wobei die Zusammensetzung anfangs eine mehraxiale Schlagenergie größer gleich 45 ft-lbs (61 Joule) zeigt und nach 300 Stunden Exposition in einem Dampfautoklav bei 130 bis 138 °C eine mehraxiale Schlagenergie größer gleich 20 ft-lbs (27 Joule) hat und die mehraxiale Schlagenergie gemäß ASTM D3763 bei 23 °C bestimmt wird;
    wobei die Zusammensetzung einen Zugmodul größer gleich 425.000 psi (2930 MPa) hat, wie mittels ASTM D638 bestimmt;
    wobei die Zusammensetzung eine Warmverformungstemperatur bei 264 psi (1,8 MPa) größer gleich 150 °C hat, wie mittels ASTM D648 an einem 3,2 Millimeter dicken Muster bestimmt; und
    wobei die Gewichtsprozente auf dem kombinierten Gewicht von Polyetherimid und Polyphenylenethersulfon basieren.
  2. Zusammensetzung nach Anspruch 1, wobei das Polyetherimid in einer Menge von 50 bis 80 Gewichtsprozent vorliegt, das Polyphenylenethersulfon in einer Menge von 20 bis 50 Gewichtsprozent vorliegt und
    die Zusammensetzung eine Warmverformungstemperatur bei 264 psi (1,8 MPa) größer gleich 175 °C hat, wie mittels ASTM D648 an einem 3,2 Millimeter dicken Muster bestimmt.
  3. Zusammensetzung nach Anspruch 2, wobei die Zusammensetzung eine prozentuale Transmission bei 3,2 Millimeter, wie mittels der ASTM-Methode D1003 gemessen, größer gleich 50 % hat.
  4. Zusammensetzung nach Anspruch 2, wobei das Polyphenylenethersulfon Grundeinheiten der folgenden Formel umfasst:
    Figure imgb0016
     wobei n > m und n + m gleich 25 bis 100 ist.
  5. Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei die Zusammensetzung eine Schmelze-Volumenfließrate, wie mittels ASTM D1238 gemessen, von 1,0 bis 25,0 cm3/10 Minuten bei 337 °C hat.
  6. Zusammensetzung nach einem der Ansprüche 1, 2, 3, 4 oder 5, wobei das Polyetherimid und das Polyphenylenethersulfon jeweils ein gewichtsmittleres Molekulargewicht (Mw) von 20.000 bis 70.000 Gramm/Mol haben und wobei der Molekulargewichtsunterschied zwischen den zwei Polymeren weniger als 20 % des höheren der Molekulargewichte beträgt.
  7. Zusammensetzung nach einem der Ansprüche 1 bis 6, wobei das Polyetherimid und das Polyphenylenethersulfon jeweils einen Brechungsindex von 1,620 bis 1,670 haben, wie mittels ASTM D542 bestimmt.
  8. Zusammensetzung nach einem der Ansprüche 1, 2 oder 4 bis 7, wobei die Zusammensetzung eine prozentuale Transmission bei 3,2 Millimeter, wie mittels der ASTM-Methode D1003 gemessen, größer gleich 50 % hat.
  9. Zusammensetzung nach einem der Ansprüche 1 bis 8, wobei größer gleich 50 Mol-% der Hauptketten-Sulfonbindungen des Polyphenylenethersulfons von Biphenol abgeleitet sind.
  10. Zusammensetzung nach einem der Ansprüche 1 bis 9, wobei das Polyetherimid eine Glasübergangstemperatur von 200 bis 280 °C hat und das Polyphenylenethersulfon eine Glasübergangstemperatur von 200 bis 250 °C hat.
  11. Zusammensetzung nach einem der Ansprüche 1 bis 10, wobei das Polyetherimid ein Polyetherimidsulfon ist.
  12. Zusammensetzung nach einem der Ansprüche 1 bis 11, wobei die Zusammensetzung weiterhin von 1 bis 30 Prozent mindestens eines Elements umfasst, bezogen auf das Gesamtgewicht der Zusammensetzung, wobei das Element aus der Gruppe bestehend aus Silikonpolyetherimid, Polyamiden, Polyphenylenethern, Polyolefinen, Polysulfonen, Polyethersulfonen und Kombinationen davon ausgewählt ist.
  13. Zusammensetzung nach einem der Ansprüche 1 bis 3 oder 5 bis 12, wobei das Polyphenylenethersulfon Grundeinheiten mit der folgenden Formel umfasst:
    Figure imgb0017
     wobei n gleich 25 bis 1000 ist, R Wasserstoff, Alkyl, Aryl, Alkylaryl, Alkoxy, Halogen oder eine Kombination davon ist und x gleich 0 bis 4 ist; und wobei die Arylsulfonbindungen aus der Gruppe bestehend aus 4,4'-Bindungen, 3,3'-Bindungen, 3,4'-Bindungen und Gemischen davon ausgewählt sind.
  14. Zusammensetzung nach einem der Ansprüche 1 bis 3 oder 5 bis 12, wobei das Polyphenylenethersulfon ein Copolymer der folgenden Struktur ist:
    Figure imgb0018
     wobei n > m, n + m gleich 25 bis 1000 ist, R Wasserstoff, Alkyl, Aryl, Alkylaryl, Alkoxy, Halogen oder eine Kombination davon ist, x gleich 0 bis 4 ist, die Arylsulfonbindungen aus der Gruppe bestehend aus 4,4'-Bindungen, 3,3'-Bindungen, 3,4'-Bindungen und Gemischen davon ausgewählt sind, A aus der Gruppe bestehend aus den folgenden ausgewählt ist: -O-, -S-, -SO2-, C6-C18-Aryl, C3-C12-Alkyl und Gemischen davon, und Bindungen von A an den Arylgruppen aus der Gruppe bestehend aus 4,4'-Bindungen, 3,3'-Bindungen, 3,4'-Bindungen und Gemischen davon ausgewählt sind.
  15. Zusammensetzung nach einem der Ansprüche 1 bis 14, wobei das Polyphenylenethersulfon ein Homopolymer, ein Copolymer oder eine Kombination davon umfasst.
EP08781489.3A 2007-07-12 2008-07-08 Polyetherimid-/polyphenylen-ether-sulfon-gemische Revoked EP2164904B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US11/776,658 US20090018242A1 (en) 2007-07-12 2007-07-12 Polyetherimide/polyphenylene ether sulfone blends
US11/853,357 US8034857B2 (en) 2007-07-12 2007-09-11 Polyetherimide/polyphenylene ether sulfone blends
PCT/US2008/069404 WO2009009525A1 (en) 2007-07-12 2008-07-08 Polyetherimide/polyphenylene ether sulfone blends

Publications (2)

Publication Number Publication Date
EP2164904A1 EP2164904A1 (de) 2010-03-24
EP2164904B1 true EP2164904B1 (de) 2016-03-30

Family

ID=39865740

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08781489.3A Revoked EP2164904B1 (de) 2007-07-12 2008-07-08 Polyetherimid-/polyphenylen-ether-sulfon-gemische

Country Status (5)

Country Link
US (1) US8034857B2 (de)
EP (1) EP2164904B1 (de)
JP (1) JP5703018B2 (de)
CN (1) CN101802099B (de)
WO (1) WO2009009525A1 (de)

Families Citing this family (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7215662B1 (en) * 2002-03-22 2007-05-08 Juniper Networks, Inc. Logical separation and accessing of descriptor memories
US20070149629A1 (en) * 2005-12-22 2007-06-28 Michael Stephen Donovan Expanded and expandable high glass transition temperature polymers
KR20120114271A (ko) 2009-12-04 2012-10-16 프루덴트 에너지 인코포레이티드 폴리머 혼합 양성자 교환막 및 이의 제조방법
US8901257B2 (en) * 2011-02-12 2014-12-02 Xerox Corporation Endless flexible members for imaging devices
WO2012167084A1 (en) * 2011-06-03 2012-12-06 Sabic Innovative Plastics Ip B.V. Sterilized polyetherimide /polyphenylene ether sulfone articles
ES2725783T3 (es) 2011-06-03 2019-09-27 Sabic Global Technologies Bv Artículos de polieterimida esterilizados
US20130053489A1 (en) 2011-08-22 2013-02-28 Robert R. Gallucci Polyetherimide compositions and methods for the manufacture and use thereof
JP6359453B2 (ja) * 2011-10-12 2018-07-18 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー ポリエーテルイミド／ポリ（ビフェニルエーテルスルホン）発泡材
US20130150504A1 (en) * 2011-12-09 2013-06-13 Sabic Innovative Plastics Ip B.V. Blends of polyphenylene ether sulfone and silicone polyester carbonate
US20140343184A1 (en) * 2011-12-22 2014-11-20 Solvay Specialty Polymers Usa, Llc. Thermoformed foam articles
EP2820113B1 (de) 2012-02-28 2017-07-12 SABIC Global Technologies B.V. Verfahren und zusammensetzungen zum reinigen von mischvorrichtungen zur verbesserung der herstellung von polycarbonat
WO2014057042A1 (en) * 2012-10-12 2014-04-17 Solvay Specialty Polymers Usa, Llc High temperature sulfone (hts) foam meterials
KR20140057108A (ko) * 2012-11-02 2014-05-12 제일모직주식회사 폴리에테르술폰계 화합물 및 그 제조방법
JP2016519190A (ja) * 2013-04-16 2016-06-30 ソルベイ スペシャルティ ポリマーズ ユーエスエー， エルエルシー 熱成形発泡体物品
US10077345B2 (en) 2013-05-31 2018-09-18 Sabic Global Technologies B.V. Capacitor films, methods of manufacture, and articles manufactured therefrom
JP6329253B2 (ja) * 2013-05-31 2018-05-23 サビック グローバル テクノロジーズ ベスローテン フェンノートシャップ コンデンサフィルム、その製造方法およびそれで製造された物品
CN105473662A (zh) * 2013-06-21 2016-04-06 索尔维特殊聚合物美国有限责任公司 增强的组合物
EP3168256B1 (de) 2013-09-26 2019-08-07 Mitsui Chemicals, Inc. Brillenmaterial enthaltend ein polyurethanharz, brillengestell und linse
WO2015095034A1 (en) 2013-12-16 2015-06-25 Sabic Global Technologies B.V. Uv and thermally treated polymeric membranes
KR20170005901A (ko) 2013-12-16 2017-01-16 사빅 글로벌 테크놀러지스 비.브이. 처리된 혼합 매트릭스 중합 멤브레인들
US10059053B2 (en) 2014-11-04 2018-08-28 Stratasys, Inc. Break-away support material for additive manufacturing
US20170084394A1 (en) * 2015-02-03 2017-03-23 Sabic Global Technologies, B.V. Polyetherimide Compatible Polymer Blends for Capacitor Films
US10221314B2 (en) 2015-03-09 2019-03-05 Sabic Global Technologies B.V. Miscible polyphenylene ether sulfone/polyalkylene terephthalate blends
JP6172586B2 (ja) * 2015-12-08 2017-08-02 住友化学株式会社 芳香族ポリスルホン樹脂及びその製造方法
DE102016209719A1 (de) * 2016-06-02 2017-12-07 Siemens Aktiengesellschaft Materialien auf Kunststoffbasis zur Verarbeitung mittels generativer Fertigungsverfahren
CN109476853A (zh) * 2016-06-20 2019-03-15 沙特基础工业全球技术有限公司 聚合物组合物、制造聚合物组合物的方法、包含聚合物组合物的制品和形成制品的方法
EP3615314B1 (de) * 2017-04-24 2021-05-19 Solvay Specialty Polymers USA, LLC Verfahren zur herstellung eines dreidimensionalen objekts mit ppsu
WO2019197587A1 (en) * 2018-04-12 2019-10-17 Solvay Specialty Polymers Usa, Llc Method for manufacturing a three-dimensional object using a nitride
JP7434992B2 (ja) * 2020-02-13 2024-02-21 三菱ケミカル株式会社 樹脂組成物及びフィルム
CN116535854B (zh) * 2023-04-26 2024-02-20 乌镇实验室 一种二元共混的高温储能聚合物介电薄膜及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1983003417A1 (en) 1982-04-02 1983-10-13 Gen Electric Polyetherimide-polysulfone blends
EP0176989A1 (de) 1984-09-28 1986-04-09 Amoco Corporation Formkörper aus Abmischungen eines Biphenylgruppen enthaltenden Poly(arylethersulfons) und eines Poly(aryletherketons)
US5037902A (en) 1988-12-30 1991-08-06 Amoco Corporation Miscible blends of imide containing polymers with poly(aryl sulfones)
US5189115A (en) 1989-02-21 1993-02-23 Amoco Corporation Polyetherimide copolymers
WO2000060009A1 (en) 1999-04-07 2000-10-12 Bp Corporation North America Inc. Poly(biphenyl ether sulfone) resins having improved uv yellowing resistance
EP1524297A1 (de) 2004-12-22 2005-04-20 Solvay Advanced Polymers, L.L.C. Sulfonpolymer-Zusammensetzung

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3847867A (en) * 1971-01-20 1974-11-12 Gen Electric Polyetherimides
US3972902A (en) * 1971-01-20 1976-08-03 General Electric Company 4,4'-Isopropylidene-bis(3- and 4-phenyleneoxyphthalic anhydride)
US3803085A (en) * 1972-12-29 1974-04-09 Gen Electric Method for making polyetherimides
US3905942A (en) * 1973-06-22 1975-09-16 Gen Electric Method for making polyetherimides and products produced thereby
US3852242A (en) * 1973-12-03 1974-12-03 Gen Electric Method for making polyetherimide
US3983093A (en) * 1975-05-19 1976-09-28 General Electric Company Novel polyetherimides
GB1586972A (en) * 1977-02-01 1981-03-25 Ici Ltd Production of aromatic polyethers
US4293670A (en) * 1979-12-26 1981-10-06 Union Carbide Corporation Blends of poly(aryl ether) resins and polyetherimide resins
US4455410A (en) * 1982-03-18 1984-06-19 General Electric Company Polyetherimide-polysulfide blends
US4443591A (en) * 1983-01-21 1984-04-17 General Electric Company Method for making polyetherimide
US4473684A (en) * 1983-04-18 1984-09-25 Union Carbide Corporation Poly (aryl ether)s
US4503168A (en) * 1983-05-25 1985-03-05 Union Carbide Corporation Cookware made from polyarylethersulfone
US5286812A (en) * 1988-02-19 1994-02-15 University Of Massachusetts High performance blends of aromatic polyimides with aromatic polyethersulfones
US5212259A (en) * 1988-12-30 1993-05-18 Amoco Corporation Miscible blends of imide containing polymers with poly(aryl sulfones)
US5134202A (en) * 1988-12-30 1992-07-28 Amoco Corporation Process for miscible blends of imide containing polymers with poly(aryl sulfones)
JPH04339860A (ja) 1990-01-30 1992-11-26 Tonen Chem Corp 熱可塑性ポリマーアロイ及びその製造方法
US5191305A (en) * 1991-07-02 1993-03-02 Interstate Electronics Corporation Multiple bandpass filter
JPH05171045A (ja) * 1991-12-18 1993-07-09 Sekisui Chem Co Ltd 樹脂組成物
JP3126214B2 (ja) * 1992-04-23 2001-01-22 積水化学工業株式会社 芳香族ポリスルホンフィルム
US5917137A (en) * 1993-10-19 1999-06-29 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Gas separation membranes of blends of polyethersulfones with aromatic polyimides
US6228915B1 (en) * 1999-04-15 2001-05-08 General Electric Company Compositions and methods for reduced food adhesion
US7041773B2 (en) * 2003-09-26 2006-05-09 General Electric Company Polyimide sulfones, method and articles made therefrom
US7902316B2 (en) * 2003-11-20 2011-03-08 Sabic Innovative Plastics Ip B.V. Polyethersulfone composition, method of making and articles therefrom
US20050113558A1 (en) * 2003-11-20 2005-05-26 General Electric Company Polyethersulfone composition, method of making and articles therefrom
US20060069236A1 (en) * 2004-09-27 2006-03-30 General Electric Company Polyethersulfone compositions with high heat and good impact resistance

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1983003417A1 (en) 1982-04-02 1983-10-13 Gen Electric Polyetherimide-polysulfone blends
EP0176989A1 (de) 1984-09-28 1986-04-09 Amoco Corporation Formkörper aus Abmischungen eines Biphenylgruppen enthaltenden Poly(arylethersulfons) und eines Poly(aryletherketons)
US5037902A (en) 1988-12-30 1991-08-06 Amoco Corporation Miscible blends of imide containing polymers with poly(aryl sulfones)
US5189115A (en) 1989-02-21 1993-02-23 Amoco Corporation Polyetherimide copolymers
WO2000060009A1 (en) 1999-04-07 2000-10-12 Bp Corporation North America Inc. Poly(biphenyl ether sulfone) resins having improved uv yellowing resistance
EP1524297A1 (de) 2004-12-22 2005-04-20 Solvay Advanced Polymers, L.L.C. Sulfonpolymer-Zusammensetzung

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"STANDARD TEST METHOD FOR HAZE AND LUMINOUS TRANSMITTANCE OF TRANSPARENT PLASTICS", ASTM DESIGNATION,, no. D1003, July 2000 (2000-07-01), XP001179974
J. RAMIRO ET AL.: "New Miscible Poly(ether imide)/Poly(phenyl sulfone) Blends", MACROMOL. MATER. ENG., vol. 291, 2006, pages 707 - 713, XP055333000

Also Published As

Publication number Publication date
JP2010532815A (ja) 2010-10-14
US8034857B2 (en) 2011-10-11
EP2164904A1 (de) 2010-03-24
CN101802099B (zh) 2012-07-11
WO2009009525A1 (en) 2009-01-15
CN101802099A (zh) 2010-08-11
JP5703018B2 (ja) 2015-04-15
US20090018265A1 (en) 2009-01-15

Similar Documents

Publication Publication Date Title
EP2164904B1 (de) Polyetherimid-/polyphenylen-ether-sulfon-gemische
US20090018242A1 (en) Polyetherimide/polyphenylene ether sulfone blends
JP5563219B2 (ja) 改良ポリアリールエーテルケトンポリマブレンド
US9181431B2 (en) Polyimide resin compositions
EP2087026B1 (de) Polymerblendzusammensetzungen
EP2714809B1 (de) Sterilisierte polyetherimid/polyphenylenethersulfonartikel
EP2089454B1 (de) Verfahren zur herstellung von polymerblendzusammensetzungen
WO2007075365A2 (en) Annular or tubular shaped articles of novel polymer blends
JP6382988B2 (ja) ポリエーテルイミドとその製造方法、および同材料からなる物品
JPH11263911A (ja) 安定化ポリエ―テルイミド樹脂組成物
EP3262117B1 (de) Zusammensetzungen mit widerstand gegen elektrische kriechwegbildung, daraus geformte artikel und verfahren zur herstellung davon
EP3262119B1 (de) Zusammensetzungen mit widerstand gegen elektrische kriechwegbildung, daraus geformte artikel und verfahren zur herstellung davon
EP3262120B1 (de) Zusammensetzungen mit widerstand gegen elektrische kriechwegbildung, daraus geformte artikel und verfahren zur herstellung davon
EP3677646B1 (de) Thermoplastische zusammensetzung, verfahren zu deren herstellung und artikel mit der thermoplastischen zusammensetzung
JP7434992B2 (ja) 樹脂組成物及びフィルム
KR20190008856A (ko) 열가소성 조성물, 이의 제조 방법 및 이로부터 제조된 물품
TW200832839A (en) High heat electrical connectors

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20091119

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL BA MK RS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: KAILASAM, GANESH

Inventor name: GALLUCCI, ROBERT R.

Inventor name: SANNER, MARK ALAN

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20111122

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20151019

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SABIC GLOBAL TECHNOLOGIES B.V.

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 785375

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160415

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602008043207

Country of ref document: DE

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160701

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160630

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160330

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 785375

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160730

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160801

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

REG Reference to a national code

Ref country code: DE

Ref legal event code: R026

Ref document number: 602008043207

Country of ref document: DE

PLBI Opposition filed

Free format text: ORIGINAL CODE: 0009260

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

26 Opposition filed

Opponent name: SOLVAY SPECIALTY POLYMERS USA, LLC

Effective date: 20161219

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PLAX Notice of opposition and request to file observation + time limit sent

Free format text: ORIGINAL CODE: EPIDOSNOBS2

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160731

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160731

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160801

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170331

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PLBB Reply of patent proprietor to notice(s) of opposition received

Free format text: ORIGINAL CODE: EPIDOSNOBS3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160708

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160708

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20170426

Year of fee payment: 11

RAP4 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: SABIC GLOBAL TECHNOLOGIES B.V.

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20080708

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

Ref country code: MT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160731

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160330

RDAF Communication despatched that patent is revoked

Free format text: ORIGINAL CODE: EPIDOSNREV1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

REG Reference to a national code

Ref country code: DE

Ref legal event code: R064

Ref document number: 602008043207

Country of ref document: DE

Ref country code: DE

Ref legal event code: R103

Ref document number: 602008043207

Country of ref document: DE

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20180626

Year of fee payment: 11

RDAG Patent revoked

Free format text: ORIGINAL CODE: 0009271

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: PATENT REVOKED

27W Patent revoked

Effective date: 20180929

GBPR Gb: patent revoked under art. 102 of the ep convention designating the uk as contracting state

Effective date: 20180929